The crystal structure of piperazinediium hexaaquazinc(II) bis(sulfate), (C4H12N2)[Zn(H2O)6](SO4)2, is built from isolated [Zn(H2O)6]2+, SO42- and C4H12N22+ ions linked together by a hydrogen-bonding network. The title compound exhibits strong analogies with some double aluminium sulfates, also known as Tutton's salts.
Supporting information
CCDC reference: 270315
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean (C-C) = 0.003 Å
- R factor = 0.044
- wR factor = 0.126
- Data-to-parameter ratio = 30.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Zn - O13 .. 6.08 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S1
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S2
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).
Piperazinediium hexaaquazinc(II) bis(sulfate)
top
Crystal data top
(C4H12N2)[Zn(H2O)6](SO4)2 | F(000) = 944 |
Mr = 453.74 | Dx = 1.795 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P_2yn | Cell parameters from 15427 reflections |
a = 12.9562 (2) Å | θ = 2.0–35.0° |
b = 10.6502 (2) Å | µ = 1.78 mm−1 |
c = 13.3251 (2) Å | T = 292 K |
β = 114.032 (1)° | Prism, colourless |
V = 1679.30 (5) Å3 | 0.20 × 0.18 × 0.15 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 7387 independent reflections |
Radiation source: fine-focus sealed tube | 5221 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 9 pixels mm-1 | θmax = 35.0°, θmin = 2.5° |
CCD rotation images, thick slices scans | h = −20→17 |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | k = −17→17 |
Tmin = 0.708, Tmax = 0.794 | l = −19→21 |
27290 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0621P)2 + 0.263P] where P = (Fo2 + 2Fc2)/3 |
7387 reflections | (Δ/σ)max = 0.001 |
244 parameters | Δρmax = 0.84 e Å−3 |
18 restraints | Δρmin = −0.82 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn | 0.495570 (17) | 0.506100 (17) | 0.241814 (16) | 0.03122 (7) | |
S1 | 0.79318 (4) | 0.37112 (4) | 0.13085 (3) | 0.02819 (9) | |
S2 | 0.24946 (4) | 0.64659 (4) | 0.39741 (3) | 0.02938 (9) | |
O1 | 0.72107 (17) | 0.48116 (15) | 0.09485 (14) | 0.0533 (4) | |
O2 | 0.91309 (12) | 0.40992 (16) | 0.17905 (11) | 0.0509 (4) | |
O3 | 0.77691 (13) | 0.28903 (13) | 0.03696 (11) | 0.0429 (3) | |
O4 | 0.76991 (14) | 0.30429 (14) | 0.21558 (13) | 0.0475 (4) | |
O5 | 0.25276 (19) | 0.51183 (13) | 0.38332 (19) | 0.0623 (6) | |
O6 | 0.25092 (13) | 0.71410 (13) | 0.30188 (11) | 0.0413 (3) | |
O7 | 0.34830 (16) | 0.6868 (2) | 0.49369 (13) | 0.0734 (6) | |
O8 | 0.14674 (14) | 0.67782 (13) | 0.41288 (15) | 0.0497 (4) | |
O11 | 0.42748 (14) | 0.41605 (13) | 0.09260 (12) | 0.0459 (4) | |
H11 | 0.383 (2) | 0.458 (2) | 0.0404 (19) | 0.055* | |
H12 | 0.406 (2) | 0.3433 (16) | 0.093 (2) | 0.055* | |
O12 | 0.60563 (14) | 0.35058 (16) | 0.29210 (13) | 0.0500 (4) | |
H21 | 0.635 (2) | 0.335 (3) | 0.3628 (14) | 0.060* | |
H22 | 0.658 (2) | 0.340 (3) | 0.270 (2) | 0.060* | |
O13 | 0.56650 (13) | 0.58934 (13) | 0.40060 (11) | 0.0411 (3) | |
H31 | 0.594 (2) | 0.5319 (18) | 0.4524 (18) | 0.049* | |
H32 | 0.6200 (18) | 0.6457 (18) | 0.422 (2) | 0.049* | |
O14 | 0.59735 (14) | 0.60520 (14) | 0.18522 (14) | 0.0459 (4) | |
H41 | 0.634 (2) | 0.564 (2) | 0.155 (2) | 0.055* | |
H42 | 0.644 (2) | 0.662 (2) | 0.224 (2) | 0.055* | |
O15 | 0.37782 (13) | 0.65604 (14) | 0.18686 (13) | 0.0435 (3) | |
H51 | 0.340 (2) | 0.676 (2) | 0.2230 (18) | 0.052* | |
H52 | 0.340 (2) | 0.666 (2) | 0.1200 (13) | 0.052* | |
O16 | 0.39560 (12) | 0.40605 (12) | 0.30433 (12) | 0.0379 (3) | |
H61 | 0.3542 (18) | 0.445 (2) | 0.3319 (19) | 0.045* | |
H62 | 0.3541 (19) | 0.3420 (18) | 0.2695 (19) | 0.045* | |
C1 | 0.59458 (18) | 1.0545 (2) | 0.08923 (17) | 0.0466 (5) | |
H1A | 0.6549 | 0.9956 | 0.0987 | 0.056* | |
H1B | 0.6251 | 1.1210 | 0.1431 | 0.056* | |
C2 | 0.4492 (2) | 0.89096 (19) | 0.02419 (19) | 0.0473 (5) | |
H2A | 0.3874 | 0.8530 | 0.0367 | 0.057* | |
H2B | 0.5041 | 0.8259 | 0.0311 | 0.057* | |
C3 | 0.54717 (18) | 0.89400 (18) | 0.57069 (16) | 0.0407 (4) | |
H3A | 0.6009 | 0.8253 | 0.5943 | 0.049* | |
H3B | 0.5032 | 0.8923 | 0.6147 | 0.049* | |
C4 | 0.38988 (17) | 0.98316 (19) | 0.41127 (17) | 0.0405 (4) | |
H4A | 0.3398 | 0.9847 | 0.4491 | 0.049* | |
H4B | 0.3442 | 0.9716 | 0.3334 | 0.049* | |
N1 | 0.47084 (13) | 0.87697 (14) | 0.45325 (13) | 0.0354 (3) | |
H1C | 0.4321 | 0.8048 | 0.4452 | 0.042* | |
H1D | 0.5124 | 0.8711 | 0.4133 | 0.042* | |
N2 | 0.50253 (15) | 0.98935 (15) | 0.10714 (14) | 0.0399 (4) | |
H2C | 0.5306 | 0.9544 | 0.1745 | 0.048* | |
H2D | 0.4498 | 1.0458 | 0.1045 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn | 0.02868 (12) | 0.03594 (12) | 0.02783 (12) | −0.00031 (7) | 0.01027 (9) | −0.00016 (7) |
S1 | 0.0285 (2) | 0.03256 (19) | 0.02380 (19) | 0.00383 (14) | 0.01090 (15) | 0.00245 (13) |
S2 | 0.0287 (2) | 0.03223 (19) | 0.0280 (2) | 0.00045 (14) | 0.01241 (16) | 0.00281 (14) |
O1 | 0.0707 (12) | 0.0523 (8) | 0.0413 (9) | 0.0306 (8) | 0.0275 (8) | 0.0145 (6) |
O2 | 0.0384 (8) | 0.0850 (11) | 0.0310 (7) | −0.0178 (7) | 0.0158 (6) | −0.0164 (7) |
O3 | 0.0436 (8) | 0.0446 (7) | 0.0362 (7) | 0.0002 (6) | 0.0118 (6) | −0.0108 (5) |
O4 | 0.0533 (9) | 0.0507 (8) | 0.0535 (9) | 0.0164 (6) | 0.0370 (8) | 0.0216 (6) |
O5 | 0.0887 (15) | 0.0330 (7) | 0.0952 (15) | 0.0124 (7) | 0.0681 (13) | 0.0099 (7) |
O6 | 0.0492 (8) | 0.0446 (7) | 0.0340 (7) | 0.0102 (6) | 0.0210 (6) | 0.0123 (5) |
O7 | 0.0515 (10) | 0.1249 (16) | 0.0311 (8) | −0.0403 (11) | 0.0039 (7) | 0.0121 (9) |
O8 | 0.0459 (9) | 0.0370 (7) | 0.0807 (11) | 0.0022 (6) | 0.0407 (9) | 0.0014 (7) |
O11 | 0.0581 (10) | 0.0376 (7) | 0.0290 (7) | −0.0065 (6) | 0.0044 (6) | 0.0020 (5) |
O12 | 0.0483 (9) | 0.0692 (10) | 0.0367 (8) | 0.0244 (7) | 0.0218 (7) | 0.0149 (7) |
O13 | 0.0440 (8) | 0.0444 (7) | 0.0296 (7) | −0.0038 (6) | 0.0097 (6) | 0.0018 (5) |
O14 | 0.0490 (9) | 0.0479 (8) | 0.0522 (9) | −0.0144 (6) | 0.0321 (8) | −0.0175 (6) |
O15 | 0.0438 (8) | 0.0509 (8) | 0.0363 (7) | 0.0137 (6) | 0.0167 (6) | 0.0075 (6) |
O16 | 0.0377 (7) | 0.0367 (6) | 0.0432 (7) | −0.0046 (5) | 0.0204 (6) | −0.0051 (5) |
C1 | 0.0374 (11) | 0.0544 (12) | 0.0375 (10) | −0.0051 (9) | 0.0047 (8) | −0.0042 (9) |
C2 | 0.0458 (12) | 0.0428 (10) | 0.0546 (13) | −0.0057 (8) | 0.0217 (10) | 0.0108 (8) |
C3 | 0.0407 (10) | 0.0445 (9) | 0.0355 (9) | 0.0020 (8) | 0.0141 (8) | 0.0086 (7) |
C4 | 0.0278 (9) | 0.0527 (11) | 0.0346 (10) | −0.0012 (7) | 0.0063 (7) | −0.0013 (7) |
N1 | 0.0319 (8) | 0.0390 (7) | 0.0375 (8) | −0.0064 (6) | 0.0165 (7) | −0.0049 (6) |
N2 | 0.0382 (9) | 0.0559 (9) | 0.0274 (7) | 0.0152 (7) | 0.0152 (7) | 0.0108 (6) |
Geometric parameters (Å, º) top
Zn—O11 | 2.0549 (14) | O15—H52 | 0.830 (16) |
Zn—O14 | 2.0571 (15) | O16—H61 | 0.868 (15) |
Zn—O16 | 2.0942 (14) | O16—H62 | 0.876 (15) |
Zn—O12 | 2.1089 (14) | C1—N2 | 1.481 (3) |
Zn—O15 | 2.1222 (14) | C1—C2i | 1.498 (3) |
Zn—O13 | 2.1268 (14) | C1—H1A | 0.9700 |
S1—O1 | 1.4531 (15) | C1—H1B | 0.9700 |
S1—O4 | 1.4661 (14) | C2—N2 | 1.475 (3) |
S1—O3 | 1.4694 (13) | C2—C1i | 1.498 (3) |
S1—O2 | 1.4779 (15) | C2—H2A | 0.9700 |
S2—O5 | 1.4503 (15) | C2—H2B | 0.9700 |
S2—O7 | 1.4598 (17) | C3—N1 | 1.483 (3) |
S2—O8 | 1.4655 (15) | C3—C4ii | 1.508 (3) |
S2—O6 | 1.4688 (13) | C3—H3A | 0.9700 |
O11—H11 | 0.830 (15) | C3—H3B | 0.9700 |
O11—H12 | 0.827 (15) | C4—N1 | 1.488 (3) |
O12—H21 | 0.877 (16) | C4—C3ii | 1.508 (3) |
O12—H22 | 0.849 (16) | C4—H4A | 0.9700 |
O13—H31 | 0.882 (15) | C4—H4B | 0.9700 |
O13—H32 | 0.872 (15) | N1—H1C | 0.9000 |
O14—H41 | 0.855 (15) | N1—H1D | 0.9000 |
O14—H42 | 0.863 (16) | N2—H2C | 0.9000 |
O15—H51 | 0.849 (15) | N2—H2D | 0.9000 |
| | | |
O11—Zn—O14 | 88.36 (6) | H51—O15—H52 | 111 (2) |
O11—Zn—O16 | 93.21 (6) | Zn—O16—H61 | 120.9 (16) |
O14—Zn—O16 | 178.25 (6) | Zn—O16—H62 | 122.1 (16) |
O11—Zn—O12 | 84.79 (6) | H61—O16—H62 | 104.1 (18) |
O14—Zn—O12 | 93.90 (7) | N2—C1—C2i | 110.19 (17) |
O16—Zn—O12 | 85.51 (6) | N2—C1—H1A | 109.6 |
O11—Zn—O15 | 93.00 (6) | C2i—C1—H1A | 109.6 |
O14—Zn—O15 | 88.02 (6) | N2—C1—H1B | 109.6 |
O16—Zn—O15 | 92.64 (6) | C2i—C1—H1B | 109.6 |
O12—Zn—O15 | 177.02 (6) | H1A—C1—H1B | 108.1 |
O11—Zn—O13 | 176.77 (5) | N2—C2—C1i | 110.48 (16) |
O14—Zn—O13 | 93.96 (6) | N2—C2—H2A | 109.6 |
O16—Zn—O13 | 84.44 (6) | C1i—C2—H2A | 109.6 |
O12—Zn—O13 | 92.81 (6) | N2—C2—H2B | 109.6 |
O15—Zn—O13 | 89.33 (6) | C1i—C2—H2B | 109.6 |
O1—S1—O4 | 109.85 (9) | H2A—C2—H2B | 108.1 |
O1—S1—O3 | 110.41 (9) | N1—C3—C4ii | 111.05 (15) |
O4—S1—O3 | 111.32 (9) | N1—C3—H3A | 109.4 |
O1—S1—O2 | 109.80 (11) | C4ii—C3—H3A | 109.4 |
O4—S1—O2 | 108.10 (9) | N1—C3—H3B | 109.4 |
O3—S1—O2 | 107.30 (9) | C4ii—C3—H3B | 109.4 |
O5—S2—O7 | 110.02 (14) | H3A—C3—H3B | 108.0 |
O5—S2—O8 | 108.61 (10) | N1—C4—C3ii | 110.28 (16) |
O7—S2—O8 | 109.37 (12) | N1—C4—H4A | 109.6 |
O5—S2—O6 | 111.15 (10) | C3ii—C4—H4A | 109.6 |
O7—S2—O6 | 107.57 (9) | N1—C4—H4B | 109.6 |
O8—S2—O6 | 110.11 (9) | C3ii—C4—H4B | 109.6 |
Zn—O11—H11 | 116.1 (19) | H4A—C4—H4B | 108.1 |
Zn—O11—H12 | 116.0 (18) | C3—N1—C4 | 111.64 (14) |
H11—O11—H12 | 113 (2) | C3—N1—H1C | 109.3 |
Zn—O12—H21 | 115.8 (17) | C4—N1—H1C | 109.3 |
Zn—O12—H22 | 121.8 (18) | C3—N1—H1D | 109.3 |
H21—O12—H22 | 106 (2) | C4—N1—H1D | 109.3 |
Zn—O13—H31 | 111.3 (17) | H1C—N1—H1D | 108.0 |
Zn—O13—H32 | 124.7 (17) | C2—N2—C1 | 111.98 (16) |
H31—O13—H32 | 102.1 (18) | C2—N2—H2C | 109.2 |
Zn—O14—H41 | 117.7 (18) | C1—N2—H2C | 109.2 |
Zn—O14—H42 | 122.4 (18) | C2—N2—H2D | 109.2 |
H41—O14—H42 | 105.4 (19) | C1—N2—H2D | 109.2 |
Zn—O15—H51 | 120.0 (17) | H2C—N2—H2D | 107.9 |
Zn—O15—H52 | 119.5 (17) | | |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O1iii | 0.83 (2) | 1.87 (2) | 2.688 (2) | 167 (3) |
O11—H12···O8iv | 0.83 (2) | 1.88 (2) | 2.7038 (19) | 177 (3) |
O12—H21···O7v | 0.88 (2) | 1.85 (2) | 2.697 (2) | 162 (2) |
O12—H22···O4 | 0.85 (2) | 1.91 (2) | 2.753 (2) | 176 (3) |
O13—H31···O5v | 0.88 (2) | 2.32 (2) | 3.073 (3) | 143 (2) |
O13—H31···O7v | 0.88 (2) | 2.46 (2) | 3.253 (3) | 150 (2) |
O13—H32···O3vi | 0.87 (2) | 1.95 (2) | 2.821 (2) | 172 (2) |
O14—H41···O1 | 0.86 (2) | 1.86 (2) | 2.709 (2) | 176 (2) |
O14—H42···O4vi | 0.86 (2) | 1.86 (2) | 2.711 (2) | 169 (3) |
O15—H51···O6 | 0.85 (2) | 1.89 (2) | 2.736 (2) | 177 (3) |
O15—H52···O3iii | 0.83 (2) | 2.08 (2) | 2.896 (2) | 168 (2) |
O16—H61···O5 | 0.87 (2) | 1.86 (2) | 2.718 (2) | 173 (2) |
O16—H62···O6iv | 0.88 (2) | 1.89 (2) | 2.7564 (19) | 172 (2) |
N1—H1C···O7 | 0.90 | 1.94 | 2.759 (2) | 151 |
N1—H1C···O6 | 0.90 | 2.54 | 3.243 (2) | 136 |
N1—H1D···O2vi | 0.90 | 1.89 | 2.766 (2) | 163 |
N2—H2C···O2vi | 0.90 | 1.85 | 2.737 (2) | 170 |
N2—H2D···O8vii | 0.90 | 1.83 | 2.724 (2) | 170 |
Symmetry codes: (iii) −x+1, −y+1, −z; (iv) −x+1/2, y−1/2, −z+1/2; (v) −x+1, −y+1, −z+1; (vi) −x+3/2, y+1/2, −z+1/2; (vii) −x+1/2, y+1/2, −z+1/2. |